EP1017660A1 - Procede de production d'aldehydes par hydroformylation en presence d'ether couronne - Google Patents

Procede de production d'aldehydes par hydroformylation en presence d'ether couronne

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Publication number
EP1017660A1
EP1017660A1 EP98948928A EP98948928A EP1017660A1 EP 1017660 A1 EP1017660 A1 EP 1017660A1 EP 98948928 A EP98948928 A EP 98948928A EP 98948928 A EP98948928 A EP 98948928A EP 1017660 A1 EP1017660 A1 EP 1017660A1
Authority
EP
European Patent Office
Prior art keywords
rhodium
aqueous phase
crown
olefin
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP98948928A
Other languages
German (de)
English (en)
Other versions
EP1017660B1 (fr
Inventor
Sandra Bogdanovic
Klaus KÜHLEIN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Celanese Sales Germany GmbH
Original Assignee
Celanese Chemicals Europe GmbH
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Filing date
Publication date
Application filed by Celanese Chemicals Europe GmbH filed Critical Celanese Chemicals Europe GmbH
Publication of EP1017660A1 publication Critical patent/EP1017660A1/fr
Application granted granted Critical
Publication of EP1017660B1 publication Critical patent/EP1017660B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions

Definitions

  • the present invention relates to a process for the hydroformylation of olefinically unsaturated compounds having 3 to 12 carbon atoms with hydrogen and carbon monoxide at elevated pressure.
  • the hydroformylation of olefins with carbon monoxide and hydrogen produces aldehydes and alcohols, the aldehydes and alcohols containing one carbon atom more than the starting oil.
  • the catalyst used is usually used in a homogeneous phase with the olefin.
  • the reaction is preferably catalyzed by hydridometal carbonyls of the metals of group VIII of the periodic table.
  • cobalt which is widely used as a catalyst metal
  • rhodium has become increasingly important for the hydroformylation of lower olefins. In contrast to cobalt, rhodium allows the reaction to be carried out at low pressure.
  • terminal olefins when terminal olefins are used, straight-chain n-aldehydes are preferably formed and iso-aldehydes only to a lesser extent.
  • the hydrogenation of the olefinic compounds to saturated hydrocarbons in the presence of rhodium catalysts is significantly lower than when using cobalt catalysts.
  • the rhodium catalyst is used in the form of modified hydridorhodium carbonyls which contain additional ligands which may be used in excess.
  • Tertiary phosphines or phosphites have proven particularly suitable as ligands.
  • Their application enables the reaction pressure to be reduced to values below 30 MPa.
  • DE-PS 27 43 630 relates to the production of Aikanpolyolen (glycols) from synthesis gas using a crown ether containing at least 4 oxygen atoms as a solvent. This crown ether is used to separate ions from the homogeneous, liquid phase without simultaneous complex formation of the rhodium-containing catalyst.
  • the reaction temperatures in all examples are above 220 ° C.
  • the problem of thermal decomposition is avoided when using two-phase catalysis.
  • the prerequisite for the use of this process is the solubility of the catalyst in the polar Phase.
  • an aqueous phase is used as the polar phase and a rhodium complex compound is used as the catalyst.
  • the solubility of the catalyst in the aqueous phase is achieved by using sulfonated triarylphosphines as complex components.
  • the catalyst is separated off from the reaction product after the hydroformylation reaction has ended simply by separating the aqueous and organic phases, ie without distillation and thus without additional thermal process steps.
  • a method is described for example in DE-PS 26 27 354.
  • a special feature of this procedure is that n-aldehydes are formed from terminal olefins with high selectivity and iso-aldehydes (ie aldehydes branched in the ⁇ position to the aldehyde group) are formed only to a minor extent.
  • carboxylated triarylphosphines are also used as complex components of water-soluble rhodium complex compounds.
  • DE 34 12 335 relates to the hydroformylation of olefins using quaternary ammonium salts.
  • a major disadvantage of using quaternary ammonium salts as amphiphilic reagents is their poor biodegradability.
  • the presence of quaternary ammonium salts in wastewater leads to considerable difficulties in wastewater treatment.
  • amphiphilic reagents or solubilizers i.e. with increasing miscibility of the aqueous catalyst phase and organic phase - the separation required for the phase separation no longer takes place or does not take place to a sufficient extent as a result of the formation of emulsions or solutions. This is particularly the case with those amphiphilic reagents that can also be used as surfactants or foaming agents.
  • the object of the invention is to provide a process for the preparation of aldehydes by hydroformylation of olefins having 3 to 12 carbon atoms, which enables higher conversions compared to the prior art and avoids the disadvantages of the prior art.
  • This object is achieved by a process for the preparation of aldehydes by reacting an olefin having 3 to 12 carbon atoms with hydrogen and carbon monoxide in the presence of a rhodium catalyst, characterized in that (a) the rhodium catalyst is in an aqueous phase, the aqueous
  • Phase is present, which is immiscible with the aqueous phase.
  • the process according to the invention is distinguished in particular by the fact that, compared to the prior art, higher conversions are achieved with a high selectivity and that no significant increase in rhodium or ligands in the organic phase and thus no increased discharge of the catalyst via the organic phase is observed .
  • the demixability of the organic phase and aqueous catalyst phase is so high that rapid separation of the organic phase and aqueous phase is ensured.
  • this process neither difficult to separate emulsions nor inseparable, homogeneous solutions are formed.
  • crown ethers are described for example in "Ullmann's Encyclopedia of Industrial Chemistry” Weinheim (1987), 5 th Ed. Volume A8 S.91-97.
  • the trisulfonated triarylphosphine is a trisulfonated triarylphosphine of the formula (I) Ar 1 SO 3 M 1
  • Ar 1 , Ar 2 and Ar 3 each independently represent a phenyl, naphthyl, biphenyl
  • M ⁇ M 2 and M 3 each independently represent an alkali metal ion or a
  • M 1 , M 2 and M 3 represent other, higher-value cations, such as, for example, alkaline earth metal or zinc cations, the charge balance essentially determining the number of these cations.
  • This trisulfonated triarylphosphine of the formula (I) is particularly preferably trisodium tris (m-sulfophenyl) phosphine of the formula
  • this trisodium salt Due to its production by sulfonation of triphenylphosphine, this trisodium salt contains portions of mono- and disulfonated compounds and small portions of the corresponding phosphine oxides.
  • the trisulfonated triarylphosphine can also be a sulfonated triarylphosphine with two phosphorus atoms, which contains, for example, a radical - (CH 2 ) X -Ar-Ar- (CH 2 ) X -, where x is an integer from 1 to 4, in particular 1 to 2, preferably 1;
  • Ar-Ar means biphenyl or binaphthyl; the - (CH 2 ) X group with one bond in each case in the ortho position to the aryl-aryl bond Ar-Ar connecting the two aryl radicals, and with the other bond in each case with one phosphorus atom, each having two further, identical or different Aryl radicals, especially phenyl radicals, is connected.
  • trisulfonated triarylphosphines containing two phosphorus atoms are compounds of the formula (II)
  • n 1 and m 2 can have the value 0 or 1, the sum of m 1 and m 2 being at least 1;
  • M 1 , M 2 , M 3 and M 4 each independently represent an alkali metal ion or an ammonium ion.
  • M ⁇ M 2 , M 3 and M 4 represent other, higher-value cations, such as, for example, alkaline earth metal or zinc cations, the charge balance essentially determining the number of these cations.
  • organic trisulfonated triarylphosphine containing two phosphorus atoms can just as well be a compound of the formula (III) in which
  • m 3l m 4l m 5 and m 6 can have the value 0 or 1, the sum of m 3 , m 4 , m 5 and m 6 being at least 2;
  • M 1 , M 2 , M 3 , M 4 , M 5 and M 6 each independently represent an alkali metal ion or an ammonium ion.
  • M 1 , M 2 , M 3 , M 4 , M 5 and M 6 to represent other, higher-value cations, such as, for example, alkaline earth or zinc cations, the charge balance essentially determining the number of these cations.
  • Such triarylphosphines of the formulas (II) and (III) containing two phosphorus atoms have in particular four to eight —SO 3 M radicals.
  • the -SO 3 M residues are usually located on the aryl radicals of the radical - (CH 2 ) X -Ar-Ar- (CH 2 ) X - and on the two further aryl radicals which are connected to the phosphorus.
  • triarylphosphines instead of sulfonated triarylphosphines, other triarylphosphines can be used as ligands in which the SO 3 M group is replaced by other groups which bring about a water solubility of the triarylphosphine, such as, for example, PO 3 M 2 groups.
  • the crown ether is selected from the group of 12-crown-4, 15-crown-5, 18-crown-6 and hydroxymethyl-18-crown-6.
  • the olefin can be selected from aliphatic, cycloaliphatic and araliphatic olefins, in particular from aliphatic and cycloaliphatic ⁇ -olefins.
  • the olefinic compound may contain one or more carbon-carbon double bonds.
  • the carbon-carbon double bond can be arranged terminally or internally.
  • Preferred are olefinic compounds with a terminal carbon-carbon double bond.
  • Examples of ⁇ -olefinic compounds (with a terminal carbon-carbon double bond) are 1-alkenes, alkylalkenoates, alkylene alkanoates, alkenylalkyl ethers and alkenols.
  • propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonen, 1-decene, 1-undecene and 1-dodecene may be mentioned as ⁇ -olefinic compounds.
  • olefins which have at most 10, preferably at most 8 carbon atoms.
  • the olefin is selected in particular from the group of propene, 1-butene, 1-pentene and 1-hexene.
  • the aqueous phase contains 20 to 500 ppm, preferably 30 to 150 ppm, in particular 40 to 100 ppm, of rhodium.
  • the ratio of rhodium to ligand can be between 1:10 and 1: 1000, preferably between 1:50 and 1: 200.
  • the aqueous phase containing the catalyst can be prepared in a comparatively simple manner by dissolving a water-soluble rhodium salt, the trisulfonated triarylphosphines and the compound of the formula (I) in water.
  • Suitable rhodium salts are, without claiming to be complete: rhodium (III) sulfate, rhodium (III) nitrate, rhodium (III) carboxylates such as rhodium (III) acetate, rhodium propionate, rhodium butyrate and rhodium-2 ethylhexanoate.
  • the aqueous phase can be used directly in the hydroformylation or it can be subjected to a preforming of the catalyst under reaction conditions beforehand in order to subsequently use it in preformed form.
  • the aqueous phase may preferably contain 2X10 "6 to 5 10 " 2 moles of rhodium per mole of olefinic compound.
  • the pressure during the reaction is generally between 20 and 150 bar, preferably between 30 and 80 bar.
  • the ratio of carbon monoxide to hydrogen can vary within wide limits. A ratio of carbon monoxide to hydrogen of 10: 1 to 1:30, in particular from 5: 1 to 1: 8, preferably from 1: 2 to 2: 1, is favorable. It is particularly preferred to inject synthesis gas in a carbon monoxide to hydrogen ratio of 1: 1.
  • the temperature during the reaction is usually between 20 and 170 ° C, preferably between 100 and 140 ° C.
  • Pressure reactors with magnetic or mechanical stirring or mixing devices are used as reaction vessels.
  • thorough mixing of the existing phases i.e. ensure of polar phase, carbon monoxide / hydrogen and possibly organic phase. This can be achieved in particular by vigorous stirring and / or pumping around the organic and aqueous phases. Continuous control of the experiment is also possible.
  • the pressure reactor is cooled, carbon monoxide and hydrogen are removed by depressurization, and the reaction mixture is removed.
  • the phases separate on their own within seconds.
  • the organic phase can be worked up by distillation and then analyzed by gas chromatography if necessary.
  • rhodium (III) acetate 60 mg (0.23 mmol) of rhodium (III) acetate are degassed in 39 ml of a 0.6 M aqueous solution of the trisodium of TPPTS (tris (metasulfonato) triphenylphosphine) corresponding to a molar ratio of rhodium to ligand of 1: 100 and 21 ml distilled water and placed in a 200 ml steel autoclave under a stream of nitrogen.
  • Example 1 (120 mmol) added.
  • the hydroformylation is carried out analogously to Example 1.a) at 125 ° C. and at 50 bar synthesis gas.
  • the composition of the product phase is determined by gas chromatography and 1 H-NMR spectroscopy and from the
  • the yield of hydroformylation product is 86.7% and the n / iso ratio is 94: 6.
  • Comparative examples 14 and 20 are carried out analogously to example 1 at 125 ° C. and 50 bar synthesis gas.
  • Examples 3 to 13, 15 to 19 and 21 to 24 according to the invention are carried out analogously to Example 2.
  • a 0.6 M aqueous solution of the trisodium salt of TPPTS (tris (metasulfonato) triphenylphosphine) corresponding to a molar ratio of rhodium to ligand of 1: 100 is used.
  • TPPTS tris (metasulfonato) triphenylphosphine
  • Olefin denotes the olefin used
  • Rh-Kat represents the amount of rhodium catalyst in mmol
  • OIJRh-Verh Stands for the molar ratio of olefin to rhodium
  • TPTS stands for the amount of 0.6 M aqueous solution of tris (metasulfonato) triphenylphosphine used in ml;
  • “Crown” stands for the crown ether used and its amount, here 12-K-4 stands for 12-Krone-4, 15-K-5 for 15-Krone-5, 18-K-6 for 18-Krone-6 and 18-K-6-OH for hydroxymethyl-18-crown-6 ((CH 2 -CH 2 -O) 5 -CH 2 - CH (CH 2 OH) O);
  • % By weight crown stands for the proportion of crown ether used, based on the catalyst phase
  • H 2 O stands for the amount of water added to the aqueous phase in ml
  • t stands for the reaction time in minutes
  • N iso
  • nb (cannot be determined) means that the ratio cannot be determined due to the low conversion.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé pour produire des aldéhydes par réaction d'une oléfine comportant 3 à 12 atomes de carbone, avec de l'hydrogène et du monoxyde de carbone en présence d'un catalyseur au rhodium. Ledit procédé est caractérisé en ce que (a) le catalyseur au rhodium est présent dans une phase aqueuse contenant i) du rhodium sous forme élémentaire ou liée, ii) une triarylphosphine trisulfonée; et iii) un éther couronne; et b) l'oléfine, dans les conditions de réaction, est présente dans une phase organique liquide non miscible avec la phase aqueuse.
EP98948928A 1997-09-25 1998-09-08 Procede de production d'aldehydes par hydroformylation en presence d'ether couronne Expired - Lifetime EP1017660B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19742305A DE19742305A1 (de) 1997-09-25 1997-09-25 Verfahren zur Herstellung von Aldehyden durch Hydroformylierung in Gegenwart von Kronenether
DE19742305 1997-09-25
PCT/EP1998/005683 WO1999015488A1 (fr) 1997-09-25 1998-09-08 Procede de production d'aldehydes par hydroformylation en presence d'ether couronne

Publications (2)

Publication Number Publication Date
EP1017660A1 true EP1017660A1 (fr) 2000-07-12
EP1017660B1 EP1017660B1 (fr) 2002-12-18

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP98948928A Expired - Lifetime EP1017660B1 (fr) 1997-09-25 1998-09-08 Procede de production d'aldehydes par hydroformylation en presence d'ether couronne

Country Status (5)

Country Link
US (1) US6388142B1 (fr)
EP (1) EP1017660B1 (fr)
DE (2) DE19742305A1 (fr)
ES (1) ES2188019T3 (fr)
WO (1) WO1999015488A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19940249A1 (de) * 1999-08-25 2001-03-01 Celanese Chem Europe Gmbh Verfahren zur Herstellung von Aldehyden
DE102008044783B4 (de) * 2008-08-28 2012-05-16 Oxea Gmbh Verfahren zur Gewinnung von aliphatischen C3- bis C10- Aldehyden aus Hochsiedern durch thermische Behandlung

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4320064A (en) * 1980-03-31 1982-03-16 Union Carbide Corporation Polynuclear rhodium carbonyl complexes
GB2085874B (en) 1980-09-04 1984-08-08 Johnson Matthey Plc Hydroformylation of olefins
US5091350A (en) * 1984-03-26 1992-02-25 Hoechst Aktiengesellschaft Process for hydroformylation with rhodium catalysts and the separation of rhodium therefrom
US4731486A (en) 1986-11-18 1988-03-15 Union Carbide Corporation Hydroformylation using low volatile phosphine ligands
DE3726128A1 (de) * 1987-08-06 1989-02-16 Ruhrchemie Ag Verfahren zur herstellung von aldehyden
DE4040315A1 (de) * 1990-12-17 1992-06-25 Hoechst Ag Verfahren zur herstellung von aldehyden
TW225485B (fr) * 1992-05-29 1994-06-21 Hoechst Ag

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9915488A1 *

Also Published As

Publication number Publication date
US6388142B1 (en) 2002-05-14
WO1999015488A1 (fr) 1999-04-01
ES2188019T3 (es) 2003-06-16
EP1017660B1 (fr) 2002-12-18
DE59806752D1 (de) 2003-01-30
DE19742305A1 (de) 1999-04-01

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